Process for breaking petroleum emulsions



,n o re orr-less iper nianent state throughout themoil :pa ed? u der-;contro1ied :.eonditiens froms mineralmnnrities no Patented Feb 20: 1951 I cation afiecelh lier. 1 la] N 0; 64,458

es p d e, d derivatives of certain resihs'hereinafter cified. Thus, the present process is concerned with breaking petroleum emulsions oi the water-in-oil type characterized byfsubjectingthe emulsion to .the action (of a hydrophilegester in which the acyl radical is that of the fattyacid of drastij complementa'ry cally-oxidized dehydrated castorcil, and the al- 11. inveritio'naisfsour companion invention 06 cer'nd lfi coholic radical s a f r n hyd phile p With the new chemical products or; compounds hydric Synthetic prduts d hydrophile synused as thecdemulsifying agents;im saidhaforethetic products being oxyalkylation products of 0 n al pha bctalvalkyleneq oxides. h

brihes' dispers'ed m a whichzzconstitutesntha continuous phase o a F k A ndvrapimprocs- 315 have been-prej- .oil rude qilsand-gelatiyelyisoitewatersmi- U v cor trolledi emulsificatipnczandv-sube- 4 seguent demulsifiqatiomuriderithezgcbnditionsjust mentio ed I f mficantmaluedim mpias. henpr's- A5 heapr venme .stemof Q moles of alkylene oxide be introduced for each phenolic nucleus; and with the final proviso that the hydrophile properties of said ester, as well as said oxyalkylated resin, in an equal weight of xylene are sumcient to produce an emulsion when said xylene solution is shaken vigorously with one to three volumes of water.

For purpose of convenience what is said herematter will be divided into four parts. Part 1 will be concerned with the production of the resin from a difunctional phenol and an aldehyde; Part 2 will be concerned with the oxyalkylation of the resin so as to convert it into a hydrophile hydroxylated derivative; Part 3 will be concerned with the conversion of the immediately aforementioned derivative into a total or partial ester by reaction with an acid, an ester, or other functional derivative, so as to obtain a compound of the kind previously specified and subsequently de-,

scribed in detail; and Part 4 will be concerned with the use of such esters as demulsifiers as hereinafter described. 1

PART 1 As to the preparation of the phenol-aldehyde resins reference is made to our co-pending applications, Serial Nos. 8,730 and 8,731, both filed February 16, 1948 (both now abandoned). In such co-pending applications we described a fusible, organic solvent-soluble, water-insoluble resin polymer of the formula In such idealized representation 11" is a numeral varying from 1 to 13 or even more, provided that the resin is fusible and organic solvent-soluble. R is a hydrocarbon radical having at least 4 and not over 8 carbon atoms. In the instant application R may have as many as 12 carbon atoms, as in the case of a resin obtained from a dodecylphenol. In the instant invention it may be first suitable to describe the alkylene oxides employed as reactants, then the aldehydes, and finally the phenols, for the reason that the latter require a more elaborate description.

The alkylene oxides which may be used are the alpha-beta oxides having not more than 4 carbon atoms, to wit, ethylene oxide, alpha-beta propylene oxide, alpha-beta butylene oxide, glyclde, and methylglycide.

Any aldehyde capable of forming a methylol or a substituted methylol group and having not more than 8 carbon atoms is satisfactory, so long as it does not possess some other functional group or structure which will conflict with the res'nification reaction or with the subsequent oxyalkyiation of the resin, but the use of formaldehyde, in it: cheapest form of an aqueous solution, for the production of the resins is particularly advantageous. Solid polymers of fo;maldehyde are more expensive and higher aldehydes are both less reactive, and are more expensive. Furthermore, the .higher aldehydes may undergo other reactions which are not desirable, thus introducing difficulties into the resinification step. Thus aoetaldehyde, for example, may undergo an aldol condensation, and it and most of the higher aldehydes enter into self-resinification ,when treated with strong acids or alkalies. On the other hand, higher aldehydes frequently beneficially affect the solubility and fusibility of a resin. This is illustrated, for example, by the difierent characteristics of the resin prepared from para-tertiary amylphenol and formaldehyde on one hand, and a comparable product prepared from the same phenolic reactant and heptaldehyde on the other hand. The former, as shown in certain subsequent examples, is a hard, brittle solid, whereas the latter is soft and tacky, and obviously easier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. The employment of furfural requires careful control for the reason that in addition to its aldehydic function, furfural can form vinyl condensations by virtue of its unsaturated structure. The production of resins from furfural for use in preparing reactants for the present process is most conveniently conducted with weak alkaline catalysts and often with alkali metal carbonates. Useful aldehydes, in addition to formaldehyde, are acetaldehyde, propionic aldehyde, butyraldehyde, Z-ethylhexanal, ethylbutyraldehyde, heptaldehyde, and benzaldehyde, furfural and glyoxal. It would appear that the use of glyoxal should be avoided due to the fact that it is tetrafunctional. However, our experience has been that, in resin manability of the other aldehydic function to enter into the reaction is presumably due to steric hindrance. Needless to say, one can use a mixture of two or more aldehydes although usually this has no advantage.

Resins of the kind which are used as intermed'ates in this invention are obtained with the use of acid catalysts or alkaline catalysts, or without the use of any catalyst at all. Among the useful alkaline catalysts are ammonia, amines, and quaternary ammonium bases. It is generally accepted that when ammonia and amines are employed as catalysts they enter into the condensation reaction and, in fact, may operate by initial combination with the aldehydic reactant. The compound hexamethylenetetramine illustrates such a combination. In light of these various reactions it becomes diflicult to present any formula which would depict the structure of the various resins prior to oxyalkylation. More will be said subsequently as to the difference between the use of an alkaline catalyst and an acid catalyst; even in the use of an alkaline catalyst there is considerable evidence to indicate that the products are not identical where different basic materials are employed. The basic materials employed include not only those previously enumerated but also the hydroxides of the alkali metals, hydroxides of the alkaline earth metals, salts of strong bases and weak acids such as sodium acetate, etc.

Suitable phenolic reactants include the following: Para tertiarybutylphenol; para-secondary-butylphenol; paratertiary-amylphenol; para-secondary-amylphenol; para-tertiary-hexylphenol; para isooctylphenol; ortho phenylphenol; para-phenylphenol; ortho-benzylphenol;

monocyclic"'islimited to the nucleus-m which the hydroxyl radical is'attache'd. Broadly speaking, where a substituent is cyclic, particularly aryl, obviously in the usual sense such phenol is actually polycyclic although the phenolic hydroxyl is not attached to a fused polycyclic nucleus. Stated another'way,'phenols inwhich the hydroxyl group is directly attached to 'a condensed or. fused polycyclic structure, are excluded. This matter, however, is clarified by the following consideration.

the following formula:

in which R is selected from the class consisting of hydrogen atoms and hydrocarbon radicals having at least 4 carbon atoms and not more than 12 carbon atoms, with the proviso that oneoccurrence of R is the hydrocarbon substituent and the other two occurrences are hydrogen atoms, and with the further provision that one or both of the 3 and positions may be methyl substituted. V

The above formula possibly can be restated more conveniently in the followingmanner, to wit, that the phenol employed is of the following formula, with the proviso that R is a hydrocarbon substituent located in the 2,4,6 position, again with the provision as to 3 or 3,5 methyl substitution.- This is conventional nomenclature, numbering the various positions in the usual clockwise manner, beginning with the hydroxyl position as one:

The manufacture of thermoplastic phenol-aldehyde resins, particularly from formaldehyde and a difunctional phenol, i. e., a phenol in which The phenols herein, contemplated for reaction may be indicated by are butylated' phenols, amylated phenols, phenylphenols, etc. The methods employed in manufacturing such resins are similar to those employed in the manufacture of ordinary phenolformaldehyde resins, in that either an acid or alkaline catalyst is usually employed. The procedure usually differs from that employed in the manufacture of ordinary phenol-aldehyde resins in that phenol, being water-soluble, reacts readily with an aqueous aldehyde solution without further difliculty, while when a water-insoluble phenol is employed some modification is usually adopted to increase the interfacial surface and thus cause reaction to take place. A common solvent is sometimes employed. I Another procedure employs rather severe agitation to create a large interfacial area. Once the reaction starts.

f to a moderate degree, it is possible that both reactants are somewhat soluble in the partially reacted mass andassist in hastening the reaction.

We have found it desirable to employ a small pro- I portion of-an organic sulfo-acid asa catalyst, either alone or along with a mineral acid like sulfuric or-hydrochloric acid. For example, alkylated aromatic sulfonic acids are effectively employed. Since commercial forms of such acids are commonly their alkali salts, it is sometimes convenient to use a small quantity of such alkali salt plus a small quantity of strong mineral acid, as shown in the examples below. If desired, such organic sulfo-acids may be prepared in situ in the phenol employed, by reacting concentrated sulfuric acid with a small proportion of the phenol. In such cases where xylene is used as a solvent and concentrated sulfuric acid is employed, some sulfonation of the xylene probably occurs to produce the sulfo-acid. Addition of a solvent such i as xylene is advantageous as hereinafter de- Lil scribed in detail. Another variation of procedure is to employ such organic sulfo-acids, in the form of their salts, in connection with an alkalicatalyzed resinification procedure. Detailed examples are included subsequently.

Another advantage in the manufacture of the thermoplastic or fusible type of resin bythe acid catalytic procedure is that, since a difunctional phenol is employed, an excess of an aldehyde, for instance formaldehyde, may be employed without too marked a change in conditions of reaction and ultimate product. There is usually little, if any, advantage, however, in using an excess over and above the stoichiometric proportions for the reason that such excess may be lost and wasted. For all practical purposes the molar ratio of formaldehyde to phenol may be limited to 0.9 to 1.2, with 1.05 as the preferred ratio, or sufficient, at least theoretically, to convert the reone of the three reactive positions (2,4,6) has' been substituted by a hydrocarbon group, and

particularly by one having at least 4 carbon atoms and not more than 12 carbon atoms, is well known. As has been previously pointed out, there is no objection to a methyl radical provided, it is maining reactive hydrogen atom of each terminal phenolic nucleus. Sometimes when higher aldehydes are used an excess of aldehydic reactant can be distilled off and thus recovered from the reaction mass. This same procedure may be used with formaldehyde and excess reactant recovered.

When an alkaline catalyst is used the amount of aldehyde, particularly formaldehyde, may be increased over the simple stoichiometric ratio of one-to-one or thereabouts. With the use of alkaline catalyst it has been recognized that considerably increased amounts of formaldehyde may be used, as much as two moles of formal-'- dehyde, for example, per mole of phenol, or even more, with the result that only a small part of suchaldehyde remains uncombined or'is subsequently liberated during resinification; Struc- OH OH.

CHg-O-CHg- Such structures may lead to the production of cyclic polymers instead of linear polymers. For this reason, it has been previously pointed out that, although linear polymers have by far the most important significance, the present invention does not exclude resins of such cyclic structures.

Sometimes conventional resinification procedure is employed using either acid or alkaline catalysts to produce low-stage resins. Such resins may be employed as such, or may be altered or converted into high-stage resins, or in any event, into resins of higher molecular weight, by heating along with the employment of vacuum so as to split off water or formaldehyde, or

' both. Generally speaking, temperatures employed, particularly with vacuum, may be in the neighborhood of 175 to 250 C., or thereabouts.

It may be well to point out, however, that the amount of formaldehyde used may and does usually affect the length of the resin chain. Increasing the amount'of the aldehyde, such as formaldehyde, usually increases the size or molecular weight of the polymer.

In the hereto appended claims there is specified, among other things, the resin polymer containing at least 3 phenolic nuclei. Such minimum molecular size is most conveniently determined as a rule by cryoscopic method using benzene, or some other suitable solvent, for instance, one of those mentioned elsewhere herein as a solvent for such resins. As a matter of fact, using the procedures herein described or any conventional resinification procedure will yield products usually havin definitely in excess of 3 nuclei. In other words, a resin having an average of 4, 5 or 5 /2 nuclei per unit is apt to be formed as a minimum in resinification, except under certain special conditions where dimerization may occur.

However, if resins are prepared at substantially higher temperatures, substituting cymene, tetralin, etc., or some other suitable solvent which boils 0r refluxes at a higher temperature, instead of xylene, in subsequent examples, and if one doubles or triples the amount of catalyst, doubles or triples the time of refluxing, uses a marked excess of formaldehyde or other aldehyde, then the average size of the resin is apt to be distinctly over the above values, for example, it may average 7 to units. Sometimes the expression low-stage resin or low-stage intermediate is employed to mean a stage having 6 or '2' units or. even less. In the appended claims we have used low-stage to mean 3 to 7 units based on average molecular weight.

The molecular weight determinations, of course, require that the product he completely soluble in the particular solvent selected as, for instance, benzene. The molecular weight determination of such solution may involve either the freezing point as in the cryoscopic method, or, less conveniently perhaps, the boiling point in an ebullioscopic method. The advantage of the ebullioscopic method is that, in comparison with the cryoscopic method, it is more apt to insure complete solubility. One such common method to employ is that of Menzies and Wright (see J. Am. Chem. Soc. 43, 2309 and 2314 (1921)). Any suitable method for determining molecular weights will serve, although almost any procedure adopted has inherent limitations. A good method for determining the molecular weights of resins, especially solvent-soluble resins, is the cryoscopic procedure of Krumbhaar which employs diphenylamine as a solvent (see Coating and Ink Resins, page 157, Reinhold Publishing Subsequent examples will illustrate the use of an acid catalyst, an alkaline catalyst, and no catalyst. As far as resin manufacture per se is concerned, we prefer to use an acid catalyst, and particularly a mixture of an organic sulfo-acid and a mineral acid, along with a suitable solvent, such as xylene, as hereinafter illustrated in detail. However, we have obtained products from resins obtained by use of an alkaline catalyst which were just as satisfactory as those obtained employing acid catalysts. Sometimes a combination of both types of catalysts is used in different stages of resinification. Resins so obtained are also perfectly satisfactory.

In numerous instances the higher molecular weight resins, i. e., those referred to as high-stage resins, are conveniently obtained by subjecting lower molecular weight resins to vacuum distillation and heating. Although such procedure sometimes removes only a modest amount or even perhaps no low polymer, yet it is almost certain to produce further polymerization. For instance, acid catalyzed resins obtained in the usual manner and having a molecular weight indicating the presence of approximately 4 phenolic units or thereabouts may be subjected to such treatment, with the result that one obtains a resin having approximately double this molecular weight. The usual prmedure isto use a secondary step, heat;-

ing the resin in the presence or absence of an inert gas, including steam, or by use of vacuum. We have found that under the usual conditions of resinification employing phenols of the kind here described,'there is little or no tendency to form binuclear compounds, i. e., dimers, resulting from the combination, for example, of 2 moles of a phenol and one mole of formaldehyde, particularly where the substituent has 4 or 5 carbon atoms. Where the number of carbon atoms in a substituent approximates the upper limit specified herein, there may be some tendency to dimerization. The usual procedure to obtain a dimer involves an enormously large excess of the phenol, for instance, 8 to 10 moles per mole of aldehyde. Substituted dihydroxydiphenylmethanes obtained from substituted phenols are not resins as that term is used herein.

Although any conventional procedure ordinarily employed many he used in the manufacture of the herein contemplated resins or, for that mater, such resins may be purchased in the open market, we have found it particularly desirable to use the procedures described elsewhere herein,

and employing a combination of an organic sulfoacid and a mineral acid as a catalyst, and xylene as a solvent. By way of illustration, certain subsequent examples are included, but it is to be understood the herein described invention is not concerned with the resins per se or withany particular method of manufacture but is concerned with the use of reactants obtained by the subsequent oxyalkylation thereof. The phenolaldehyde resins may be prepared in any suitable manner.

Oxyalkylation, particularly oxyethylation which is the preferred reaction, depends on contact between a non-gaseous phase and a gaseous phase. It can, for example. be carrie out by melting the thermoplastic resin and subjecting it to treatment with ethylene oxide or the like, or by treating a suitable solution or suspension Since the melting points of the reins are often higher than desired in the initial stage of oxyethylation, we have found it advantageous to use a solution or suspension of thermoplastic resin in an inert solvent such as xylene. Under such circumstances, the resin obtained in the usual manner is dissolved by heating in xylene under a reflux condenser or in any other suitable man- Since xylene or an equivalent inert olvent is present or may be present during oxyalkylation. it is obviousthere is no objection to having a solvent present during the resinifying stage if, in addition to being inert towards the re in, it is also inert towards the reactants and al o inert towards water. Numerous solvents, particularly of aromatic or cyclic nature, are suitably adapted for such use. Examples of such solvents are xylene, cymene, ethyl benzene, propyl benzene, mesitylene, decalin (decahydronaphthalene), tetralin (tetrahydronaphthalene) ethylene glycol diethylether, diethylene glycol diethylether, and tetraethylene glycol dimethylether, or mixtures of one or more. Solvents such as dichloroethylether, or dichloropropylether may be employed either alone or in mixture but have the objection that the chlorine atom in the compound may slowly combine with the alkaline catalyst employed in oxyethylation. Suitable solvents may be selected from this group for molecular weight determinations. I

The use of such solvents is a convenient expedient in the manufacture of the thermoplastic resins, particularly since the solvent gives a more liquid reaction mass and thus prevents overheating, and also because the solvent can be employed in connection with a reflux condenser and a water trap to assist in the removal of water of reaction and also water present as part of the formaldehyde reactant when an aqueous solution of formaldehyde is used. Such aqueous solution, of course, with the ordinary productof commerce containing about 37 to 40% formaldehyde, is the preferred'reactant. When such solvent is used it is advantageously added at the beginning of theresinification procedure or before the reaction has proceeded very far.-

The solvent can be removed afterwards by distillation with or without the use of vacuum, and

a final higher temperature can be employed to complete reaction if desired. In many instances it is most desirable to permit part of the solvent,

particularly when it is inexpensive, e. g., xylene, to remain behind in a predeterminedamount. so as to have a resin which can. be handled more conveniently in the oxyalkylation stage. If a more expensivesolvent, such as decalin, is employed, xylene or other inexpensive solvent may be added after the removal of decalin, if desired.

. In preparing resins from difunctional phenols it is' common to employ r'ractants of technical grade. The substituted phenols herein contemplated are usually derived from hydroxybenzene. As a rule, such substituted phenols are comparatively free from unsubstituted phenol. We have generally found that the amount present is considerably less than 1% and not infrequ ntly in the neighborhood of 1 s of 1%, or even less. The amount of the usual trifunctional phenol, such as hydroxybenz ne or metacresol, which can be tolerated is determined by the fact that actual cross-linking, if it takes place even infrequently, must not be sufficient to cause insolubility at the completion of the resinification stage or the lack of hydroph le properties at the completion of the oxyalkylation sta e.

The exclusion of such trifunctional phenols as hydroxybenzene or metacresol is not based on the fact that the mere random or occasional inclusion of an unsubstituted phenyl nucleus in the resin molecule or in one of several molecules, for example, markedly alters the characteristics of the oxyalkylated derivative. The presence of a phenyl radical having a reactive hydrogen atom available or having a hydroxymethylol or a substituted hydroxymethylol group present is a potential source of cross-linking either during resinification or oxyalkylation. Cross-linking leads either to insoluble resins or to non-hydrophilic products resulting from the oxyalkylation procedure. With this rationale understood, it is obvious that trifunctional phenols are tolerable only in a minor proportion and should not be present to the extent that insolubility is pro duced in the resins, or that the product resulting from oxyalkylation is gelatinous, rubbery, or at least not hydrophile. As to the rationale of resinification, note particularly what is said hereafter in differentiating between resoles, Novolaks, and resins obtained solely from difunctional phenols.

Previous reference has been made to the fact that fusible organic solventsoluble resins are usually linear but may be cyclic. Such more complicated structure may be formed, particularly if a resin prepared in the usual manner is converted into a higher stage resin by heat treatment in vacuum as previously mentioned. This again'is a reason for avoiding any opportunity for cross-linking due to the presence of any appreciable amount of trifunctional phenol. In other words, the presence of such reactant may cause cross-linking in a conventional resinification procedure, or in the oxyalkylation procedure, or in the heat and vacuum treatment if it is employed as part of resin manufacture.

Our routine procedure in examining a phenol for suitability for preparing intermediates to be used in practicing the invention is to prepare a hyde,

fies as being hydrophile as herein specified.

Increasing the size of the aldehydic nucleus, for instance using heptaldehyde instead of formaldeincreases tolerance for trifunctional phenol.

The presence of a trifunctional or tetrafuhctional phenol (such as resorcinal or bisphenol A) is apt to produce detectable cross-linking and insolubilization but will not necessarily do so, especially if the proportion is small. Resinification involving difunctional phenols only may also produce insolubilization, although this seems to be an anomaly or a contradiction of what is sometimes said in regard to resinification reactions involving difunctional phenols only. This is presumably due to cross-linking. This appears to be contradictory to what one might expect in light of the theory of functionality in resinification It is true that under ordinary circumstances, or rather under the circumstances of conventional resin manufacture, the procedures employing difunctional phenols are very apt to, and almost invariably do, yield solvent-soluble, fusible resins.

However, when conventional procedures are employed in connection with resins for varnish manufacture or the like, there is involved the matter of color, solubility in oil, etc. When resins of the same type are manufactured for the herein contemplated purpose, i. e., as a raw material to be subjected to oxlalkylation, such criteria of selection are no longer pertinent. Stated another way, one may use more drastic conditions of resinification than those ordinarily employed to produce resins for the present purposes. Such more drastic conditions of resinification may include increased amounts of catalyst, higher temperatures, longer time of reaction, subsequent reaction involving heat alone or in combination with vacuum, etc. Therefore, one is not only concerned with the resinification reactions which yield the bulk of ordinary resins from difunctional phenols but also and particularly with the minor reactions of ordinary resin manufacture which are of importance'in the present invention for the reason that they occur under more drastic conditions of resinification which may be employed advantageously at times, and they may lead to cross-linking.

In this connection it may be well to point out that part of these reactions are now understood or explainable to a greater or lesser degree in light of a most recent investigation. Reference is made to the researches of Zinke and his coworkers, Hultzsch and his associates, and to von Eulen and his co-workers, and others. As to a bibliography of such investigations, see Carswell,

12 of it is referring to resinification involving difunctional phenols.

For the moment, it may be simpler to consider a "most typical type of fusible resin and forget for the time .that such resin, at least under certain circumstances, is susceptible to further complications. Subsequently in the text it will be pointed out that cross-linking or reaction with excess formaldehyde may take place even with one of such most typical type resins. This point is made for the reason that insolubles must be avoided in order to obtain the products herein contemplated for-use as reactants.

The typical type of fusible resin obtained from a para-blocked or ortho-blocked phenol is clearly difierentiated from the Novolak type or resole type of resin. Unlike the resole type, such typical type para-blocked or ortho-blocked phenol resin may be heated indefinitely without passing into an infusible stage, and in this respect is similar to a Novolak. Unlike the Novolak type the addition of a further reactant, for instance, more aldehyde, does not ordinarily alter fusibility of the difunctional phenol-aldehyde type resin; but such addition to a Novolak causes cross-linking by virtue of the available third functional position.

What has been said immediately preceding is subject to modification in this respect: It is well known, for example, that difunctional phenols, for instance, paratertiaryamylphenol, and an aldehyde, particularly formaldehyde, may yield heat-hardenable resins, at least under certain conditions, as for example the use of two moles of formaldehyde to one of phenol, along with an alkaline catalyst. This peculiar hardening or curing or cross-linking of resins obtained from difunctional phenols has been recognized by various authorities.

The intermediates herein used must be hydrophile or sub-surface-active or surface-active as hereinafter described, and this precludes the formation of insolubles during resin manufacture or the subsequent stage of resin manufacture where heat alone, or heat and vacuum, are employed, or in the oxyalkylation procedure. In its simplest presentation the rat onale of resinification involving formaldehyde, for example, and a difunctional phenol would not be expected to form cross-links. However, cross-linking sometimes occurs and it may reach the objectionable stage. However, provided that the preparation of resins simply takes into cognizance the present knowledge of the subject, and employing preliminary, exploratory routine examinations as herein indicated, there is not the slightest diiliculty in preparing a very large number of resins of various types and from various reactants, and by means of different catalysts by different procedures, all of which are eminently suitable for the herein described purpose.

Now returning to the thought that cross-linking can take place, even when difunctional phenols are used exclusively, attention is directed to the following: Somewhere during the course of resin manufacture there may be a potential crosslinking combination formed but actual crosslinking may not take place until the subsequent stage is reached, i. e., heat and vacuum stage, or oxyalkylation stage. This situation may be related or explained in terms of a theory of flaws, or Lockerstellen, which is employed in explaining flaw-forming groups due to the fact that a CHzOH'radical and H atom may not-lie in the same plane in the manufacture of ordinary phe pol-aldehyde resins.

Secondly, the'formation or absenceof forma .7

tion of insolubles may be related to the aldehyde used and the ratio of aldehyde, particularly.form-' aldehyde, insofar that a slight variation may, under circumstances not understandable, produce,

insolubilization. The formation of the insoluble resin is apparently very sensitive to the quantity,

of formaldehyde employed and a slight increase in the proportion of formaldehyde may lead to the formation of insoluble gel lumps. The cause of insoluble resin formation is not clear, and nothing is known as to the structure of these resins.

, tants, are water-insoluble, or have no appreme, fusible not necessarily thermoplastic i the most rigid sense that such terminology would beapplied to the mechanical properties of a resin, are usefulintermediates. The bulk of all fusible'resinsof the kind hereindescribed are ciable hydrophile' properties. The hydrophile' property is introduced by oxyalkylation. In the hereto appendedclaims and elsewhere the expression water-insoluble is used All that has :been said previously herein as I regards resinification has avoided the specific reference to activity of a methylene hydrogen atom. Actually there is a possibility that under some drastic conditions cross-linking may take place through formaldehyde addition to the methylene bridge, or some other reaction involving a methylene hydrogen atom.

Finally, there is some evidence that, although the meta positions are not ordinarily reactive, possibly at times, methylol groups or the like are formed at the meta positions; and if this were the case it may be a suitable explanation of abnormal cross-linking. Reactivity of a resin towards excess aldehyde, for instance formaldehyde, is not to be taken as a criterion of rejection for use as a reactant. In other words, a phenol-aldehyde resin which is thermoplastic and solventsoluble. particularly if xylene-soluble, is perfectly satisfactory even though retreatment with more aldehyde may change its characteristics markedly in regard to both fusibility and solubility. Stated another way, as far as resins obtained from difunctional phenols are concerned, they may be either formaldehyde-resistant 'or not formaldehyde-resistant.

Referring again to the resins herein contemplated as reactants, it is to be noted that they are thermoplastic phenol-aldehyde resins derived from difunctional phenols and are clearly distinguished from Novolaks or resoles. When these resins are produced from difunctional pheployed, particularly for demulsification, it is obvious that the resins can be obtained by one-of a number of procedures. In the first place, suitable, resins are marketed by a number of companies and can be purchased in the open market; in the second place, there are a wealth of examples of suitable resins described in. the literature. The third procedure is to follow the directions of the present application.

The polyhydric reactants, -i. e., the oxyalkylation-susceptible, water-insoluble, organic solvent-soluble, fusible, phenol-aldehyde resins denols and some of the higher aliphatic aldehydes,

such as acetaldehyde, the resultant is often a comparatively soft or pitchlike resin at ordinary temperature. Such resins become comparatively fluid at to C. as a rule and thus can be readily oxyalkylated, preferably oxyethylated, without the use of a solvent.

Reference has been made to the use of the word fusible. Ordinarily a thermoplastic resin is identified asone which can be heated repeatedly and still not lose its thermoplasticity. It is recognized, however, that one may have a resin which is initially thermoplastic :but on repeated heating may become insoluble in an organic solvent, or at least no longer thermoplastic, due to the fact that certain changes take place very slowly. As far as the present invention is concerned, it is obvious that a resin to be suitable need only be sufficiently fusible to permit proc-' essing to produce our oxyalkylated products and not yield insolubles or cause insolubilization or gel formation, or rubberiness, as previously 'described. Thus resins which are, strictly speakrived-from difunctional'phenols, used as intermediates to'produce the products used in accordance with the invention, are exemplified by Examples Nos. la through 103a of our Patent 2 449,370, granted March 7, 1950, and reference is made to that patent for examples of the oxyalkylated resins used as intermediates.

Previous reference, has been made to the use of a single phenol as herein specified, or a single reactive aldehyde, or a single oxyalkylating agent. Obviously, mixtures of reactants may be employed, as for example a mixture of parabutylphenol and para-amylphenol, or a mixture of 'para-butylphenol and para-hexylphenol, or para-butylphenol'and para-phenylphenol. It is extremely difficult to depict the structure of a resin derived from a single phenol. When mix tures of phenols are used, even in equimolar proportions, the structure of the resin is even more indeterminable. In other words, a mixture in-' volving para-butylphenol and para amylphenol might have an alternation of the two nuclei or one might have a series of butylated' nuclei and then a series of amylated nuclei. If a mixture of aldehydes is employed, for instance, acetaldehyde and butyraldehyde, or acetaldehyde and formaldehyde, or benzaldehyde and acetalde- 1 hyde, the final structure of the resin becomes even more complicated and possibly depends on the relative reactivity of the aldehydes. For that matter, .one might be producing simultaneously two different resins, in What would actually be a mechanical mixture, although such mixture might exhibit some unique properties as compared with a mixture of the same two resins prepared separately. Similarly, as has been suggested, one might use a combination of oxyalkylating agents; for instance, one might partially oxyalkylate with ethylene oxide and then finish off with propylene oxide. It is understood that theoxyalkylated derivatives of such resins, derived from such plurality of reactants, instead of being limited to a single reactant from each of the three classes, is contemplated and here included for the reason that they are obvious variants. I

w to point out this characteristic of the resins used. I In the manufacture of-compounds herein em PART 2 Having obtained a suitable resin of the kind described, such resin is subjected to treatment with a low molal reactive alpha-beta olefin oxide so as to render the product distinctly hydrophile in nature as indicated by the fact that it becomes self-emulsifiable or miscible or soluble in -water, or self-dispersible, or has emulsifying properties. The olefin oxides employed are characterized by the fact that they contain not over 4 carbon atoms and are selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylglycide. Glycide may be, of course, considered as a hydroxy propylene oxide and methyl glycide as a hydroxy butylene oxide. In any event, however, all such reactants contain the reactive ethylene oxide ring and may be best considered as derivatives of or substituted ethylene oxides. The solubilizing effect of the oxide is directly proportional to the percentage of oxygen present, or specifically, to the oxygen-carbo ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is 2:3; and in methyl glycide, 1:2. In such compounds, the ratio is very favorable to the production of hydrophile or surfaceactive properties. However, the ratio, in propylene oxide, is 1:3, and in butylene oxide, 1:4. Obviously, such latter two reactants are satisfactorily employed only where the resin composition is such as to make incorporation of the desired property practical. In other cases, they may produce marginally satisfactory derivatives, or even unsatisfactory derivatives. They .are usable in conjunction with the three more favorable alkylene oxides in all cases. For instance, after one or several propylene oxide or butylene oxide molecules have been attached to the resin molecule, oxyalkylation may be satisfactorily continued using the more favorable members of the class, to produce the desired hydrophile product. Used alone, these two reagents may in some cases fail to produce sufficiently hydrophile derivatives because of their relatively low oxygen-carbon ratios.

Thus, ethylene oxide is much more effective than propylene oxide, and propylene oxide is more effective than butylene oxide. Hydroxy propylene oxide (glycide) is more effective than propylene oxide. Similarly, hydroxy butylene oxide (methyl glycide) is more effective than butylene oxide. Since ethylene oxide is the cheapest alkylene oxide available and is reactive, its use is definitely advantageous, and especially in light of its high oxygen content. Propylene oxide is less reactive than ethylene oxide, and butylene oxide is definitely less reactive than propylene oxide. On the other hand, glycide may react with almost explosive violence and must be handled with extreme care.

The oxyalkylation of resins of the kind from which the initial reactants used in the practice of the present invention are prepared is advantageously catalyzed by the presence of an alkali.

Useful alkaline catalysts include soaps, sodium acetate, sodium hydroxide, sodium methylate, caustic otash, etc. The amount of alkaline catalyst usually is between 0.2% to 2%. The temperature employed may vary from room temperature to as high as 200 C. The reaction may be conducted with or without pressure, i. e., from zero pressure to approximately 200 or even 300 pounds gauge pressure (pounds per square inch). In a general way, the method employed is substantially the same procedure as used for oxyalkylation of other organic materials having reactive phenolic groups.

It may be necessary to allow for the acidity of a resin in determining the amount of alkaline catalyst to be added in oxyalkylation. For instance, if a nonvolatile strong acid such as sulfuric acid is used to catalyze the resinification reaction, presumably after being converted into a sulfonic acid, it may be necessary and is usually advantageous to add an amount of alkali equal stoichiometrically to such acidity, and include added alkali over and above this amount as the alkaline catalyst.

It is advantageous to conduct the oxyethylation in presence of an inert solvent such as xylene, cymene, decalin, ethylene glycol diethylether, diethyleneglycol diethylether, or the like, although with many resins, the oxyalkylation proceeds satisfactorily without a solvent. Since xylene is cheap and may be permitted to be present in the final product used as a demulsifier, it is our preference to use xylene. This is particularly true in the manufacture of products from low-stage resins, i. e., of 3 and up to and including 7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated, the pressure readings of course represent total pressure, that is, the combined pressure due to xylene and also due to ethylene oxide or whatever other oxyalkylating agent is used. Under such circumstances it may be necessary at times to use substantial pressures to obtain effective results, for instance, pressures up to 300 pounds along with correspondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solvent such as xylene can be eliminated in either one of two ways: After the introduction of approximately 2 or 3 moles of ethylene oxide, for example, per phenolic nucleus, there is a definite drop in the hardness and melting point of the resin. At this stage, if xylene or a similar solvent has been added, it can be eliminated by distillation (vacuum distillation if desired) and the subsequent intermediate, being comparatively soft and solvent-free, can be reacted further in the usual manner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with such solvent present and then eliminate the solvent by distillation in the customary manner.

Another suitable procedure is to use propylene oxide or butylene oxide as a solvent as well as a reactant in the earlier stages along with ethylene oxide, for instance, by dissolving the powdered resin in propylene oxide even though oxyalkylation is taking place to a greater or lesser degree. After a solution has been obtained which represents the original resin dissolved in propylene oxide or butylene oxide, or a mixture which includes the oxyalkylated product, ethylene oxide is added to react with the liquid mass until hydrophile properties are obtained. Since ethylene oxide is more reactive than propylene oxide or butylene oxide, the final product may contain some unreacted propylene oxide or butylene oxide which can be eliminated by volatilization or distillation in any suitable Attention is directed to the fact that the resins herein described must be fusible or soluble in an organic solvent. Fusible resins invariably are soluble in one or more organic solvents such as 17 those mentioned elsewhere herein. It is to be emphasized. however, that the organic solvent employed to indicate or assure that the resin meets this requirement need not be the one used in oxyalkylation. Indeed, solvents which are susceptible to oxyalkylation are included in this group of organic solvents. Examples of such solvents are alcohols and alcohol-ethers. However, where a resin is soluble in an organic solvent, there are usually available .other organic solvents which are not susceptible to oxyalkylation, useful for the oxyalkylation step. In any event, the organic solvent-soluble resin can be finely powdered, for instance to 100 to 200 mesh,

and a slurry orsuspension prepared in xylene or the like, and subjected to oxyalkylation. The fact that the resin. is soluble in an organic solvent or the'fact thatit is: fusible means that it consists of separate molecules. Phenol-aldehyde resins ofrtheitype herein specified possess reactive hydroxylgroups and are oxyalkylation susceptible. Considerableof what is said immediately hereinafter is concerned with ability to vary the hydrophile properties of the hydroxylated intermediate reactants from minimum hydrophile properties to maximum hydrophile properties.

Such properties in turn, of course, are eifected subsequently by the acid employed for esterification and the quantitative nature of the esterification itself, i. e., whether it is total or partial.

It may be well, however, to point out whathas been said elsewhere in regard to the hydroxylated intermediate reactants. See, for example, our co-pending applications, Serial Nos. 8730 and 8731, both filed February 16, 1948, and Serial No. 42,133, filed August 2, 1948 (all three cases now abandoned), and :Serial No. 42,134, filed August 2, 1948. The reason is that the esterification, depending on thez'acid selected, may vary the hydrophile-hydrophobe balance in one direction or the other, and also invariably causes the development of some property which makes it inherently'difierent from the two reactants from which the derivative ester is obtained.

Referring to the hydrophile hydroxylated intermediates, even. more remarkable and equally .diilicult to explain, are the versatility and the .-utility .of these. compounds considered as chemical reactants as one goes from minimum hydrophilepropertyto ultimate maximum hydrophile property. For instance, minimum hydrophile property may be described roughly as the point where two ethyleneoxy radicals or moderately in excess thereof are introduced per phenolic hydroxyl. Such minimum hydrophile property or fsub-surface-activity or minimum surface-activitymeans that the product shows at least emulsifying properties or self-dispersion in cold oreven in warm distilled water (1512; 40 C.) in concentrations of 0.5% to 5.0%.- These materials are I generally more soluble in cold water than warm water, and may even be very insoluble in boiling water. Moderately high temperatures aid in reducing the viscosity of the solute under examination. Sometimes if one continues to shake a hot solution, even though cloudy or containing an insoluble phase, one finds that solution takes place to give a homogeneous phase as the mixture cools. Such self-dispersion tests are conducted in the absence of an insoluble solvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2 moles of ethylene oxide per phenolic nucleus or the equivalent) but insufllcient to give a $01 as described immediately preceding, then, and in that event hydrophile properties are indicated by the fact that 75 ell one can produce an emulsion by having present 10% to 50% of an inert solvent such as xylene. All that one need to do is to have a xylene solution within the range of 50 to 90 parts by weight of oxyalkylated derivatives and 50 to 10 parts by weight of xylene and mix such solution with one, two or three times its volume of distilled water and shake vigorously so as to obtain an emulsion which may be of the oil-in-water type or the water-in-oil type (usually the former). but, in any event, is due to the hydrophile-hydrophobe balance of the oxyalkylated derivative. We prefer simply to use the xylene diluted derivatives, which are described elsewhere, for this test rather than evaporate the solvent and employ any more elaborate tests, if the solubility is not 'suflicient to'permit the simple sol test in water previously noted. If the product is not readily water soluble it may be dissolv-d in ethyl or methyl alcohol.

ethylene glycol diethylether, or diethylene glycol diethylethen with a little acetone added if required, making a rather concentrated solution.

' for instance 40% to 50%, and then adding enough of the concentrated alcoholic or equivalent solution to give the previously suggested 0.5 to 5.0% strength solution. If the product is self-dispersing (i. e., if the oxyalkylated product is a liquid or a liquid solution self-emulsifiable),tsuch sol or dispersion is referred to as at least semi-stable in the sense that sols, emulsions, or dispersions prepared are relatively stable, if they remain at least for some period of time, for instance 30 minutes to two hours. before showing any marked separation. Such tests are conducted at room temperature (22 C.). Needless to say, a test can be made in presence of an insoluble solvent such as 5% to 15% of xylene, asnoted in previous examples. If such mixture, 1. e., containing a water-insoluble solvent, is at least semi stable, obviously the solvent-free product would be even more so. Surface-activity representing an advanced hydrophile-hydrophobe balance can also be determined by the use of conventional.

, measurements hereinafter described. One out-' standing characteristic property indicating surface-activity in a material is the ability to form a permanent foam in dilute aqueous solution, for.

. example, less than 0.5%, when in the higher oxy- Y hydric reactants, is based on the conversion of a hydrophoba or non-hydrophile compound or mixture of compounds into products which are distinctly hydrophile, at least to the extent that suits are obtained witnproducts which do not have hydrophile properties beyond the stage of self-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols which show typical properties comparable to ordinary surface-active agents. Such conventional surface-activity may be measured by determining the surface tension and the interfacial tension against parafiln oil or the like. At the initial and lower stages of oxyalkylation, surface-activity is not suitably determined in this same manner but one may employ an tmulsification test. Emulsions come into existence as a rule through the presence of a surface-active emulsifying agent. Some surfaceactive emulsifying agents such as mahogany soap may produce a water-in-oil emulsion or an oilin-water emulsion depending upon the ratio of the two phases, degree of agitation, concentration of emulsifying agent, .etc.

The same is true in regard to the oxyalkylated resins herein specified, particularly in the lower stage of oxyalkylation, the so-called sub-surface-active stage. The surface-active properties are readily demonstrated by producing a xylene-water emulsion. A suitable procedure is as follows: The oxyalkylated resin is dissolved in an equal weight of xylene. Such 50-50 solution is then mixed with 1-3 volumes of water and shaken to produce an emulsion. The amount of xylene is invariably sufiicient to reduce even a tacky resinous product to a solution which is readily dispersible. The emulsions so produced are usually xylene-in-wat-r emulsions (oil-inwater type) particularly when the amount of distilled water used is at least slightly in excess of the volume of xylene solution and also if shaken vigorously. At times, particularly in th lowest stage of oxyalkylation, one may obtain a waterin-xylene emulsion (water-in-oil type) which is apt to reverse on more vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained from para-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1 formaldehyde) using an acid catalyst and then followed by oxvalkylation using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful. Such resin prior to oxyalkylation has a molecular weight indicating about 4 units per resin molecule. Such resin, when diluted with an equal weight of xylene, will serve to illustrate the above emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylene alone but may require the addition of some ethylene glycol diethylether as described elsewhere. It is understood that such mixture, or any other similar mixture, is considered the equivalent of xylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence of hydrophile or surfaceactive characteristics in the polyhydric reactants used in accordance with this invention. They dissolve or disperse in water; and such dispersions foam readily. With borderline cases, i. e., those which show only incipient hydrophile or surface-active property (sub-surface-actlvity) tests for emulsifying properties or self-dispersibilit'. are useful. The fact that a reagent is capable of producing a dispersion in water is proof that it is distinctly hydrophile. In doubtful cases, comparison can be made with the butylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxide have been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may mask the point at which a solvent-free product on mere dilution in a test tube exhibits self-emulsification. For this reason.

if it is desirable to determine the approximate point where self-emulsiflcation begins, then it is better to eliminate the xylene or equivalent from a small portion of the reaction mixture and test such portion. In some cases, such xylenefree resultant may show initial or incipient hydrophile properties, whereas in presence of xylene such properties would not be noted. In other cases, the first objective indication of hydrophile properties may be the capacity of the material to emulsify an insoluble solvent such as xylene. It is to be emphasized that hydrophile properties herein referred to are such as those exhibited by incipient self-emulsification or the presence of emulsifying properties and go through the range of homogeneous dispersibility or admixture with water even in presence of added water-insoluble solvent and minor proportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsiflcation test may be used to determine ranges of surface-activity and that such emulsificatlon tests employ a xylene solution. Stated another way, it is really immaterial whether a xylene solution produces a sol or whether it merely produces an emulsion.

In light of what has been said previously in regard to the variation of range of hydrophile properties, and also in light of what has been said as to the variation in the effectiveness of various alkylene oxides, and most particularly of all ethylene oxide, to introduce hydrophile character, it becomes obvious that there is a wide variation in the amount of alkylene oxide employed, as long as it is at least 2 moles per phenolic nucleus, for producing products useful for the practice of this invention. Another variation is the molecular size of the resin chain resulting from reaction between the difunctional phenol and the aldehyde such as formaldehyde. It is well known that the size and nature or structure of the resin polymer obtained varies somewhat with the conditions of reaction, the proportions of reactants, the nature of the catalyst, etc.

Based on molecular weight determinations, most of the resins prepared as herein described, particularly in the absence of a secondary heating step, contain 3 to 6 or 7 phenolic nuclei with approximately 4 or 5% nuclei as an average. More drastic conditions of resinification yield resins of greater chain length. Such more intensive resinification is a conventional procedure and may be employed if desired. Molecular weight, of course, is measured by any suitable procedure, particularly by cryoscopic methods; but using the same reactants and using more drastic conditions of resinification one usually finds that higher molecular weights are indicated by higher melting points of the resins and a tendency to decreased solubility. See what has been said elsewhere herein in regard to a secondary step involving the heating of a resin with or without the use of vacuum.

We have previously pointed out that either an alkaline or acid catalyst is advantageously used in preparing the resin. A combination of catalysts is sometimes used in two stages; for instance, an alkaline catalyst is sometimes employed in a first stage, followed by neutralization and addition of a small amount of acid catalyst in a second stage. It is generally believed that even in the presence of an alkaline catalyst. the number of moles of aldehyde, such as formaldehyde,.must be greater than the moles of phenol employed in order to introduce methylol firm this fact in an examination of a large number of resins prepared by ourselves. erence, however, is to use an acid-catalyzed resin. riarticularlr m loyin a formaldehyde-toplienol ratio of 0.95 to 1.20 and, as far as we have been able to determine, such resins are free from methylol groups. As a matter of fact, it is probable that in acid-catalyzed resiniflcations,

I the methylol structure may appear only momentarily at the very beginning of the reaction and Our pref- 22 resins are produced from difunctional phenols and some of the higher aliphatic aldehydes, such as acetaldehyde, theresultant is a comparatively soft or pitch-like resin at ordinary temperatures. Such resins become comparatively fluid at 110 to 165 C. as a rule, and thus can be readily oxyalkylated, preferably oxyethylated. without the use of a solvent.

What has been said previously not intended to suggest that any experimentation is necessary to determine the degree of oxyalkylation, and

. particularly oxyethylation. What has been said previously is' submitted primarily to emphasize in all probability is converted at once into a more complex structure during the intermediate stage. One procedure which can be employed in the use of a new resin to prepare polyhydric reactants for use in the preparation of compounds employed in the present invention, is to determine the hydroxyl value by the Verley-Biilsing method or its equivalent. The resin as such, or in the form of a solution as described, is then treated with ethylene oxide in presence of 0.5% to 2% of sodium methylate as a catalyst in stepwise fashion. The conditions of reaction, as far as time or per cent are concerned, are within the range previously indicated. With suitable agitation the ethylene oxide, if added in molecular proportion, combines within a comparatively short time, for instance a few minutes to 2 to 6 hours, but in some instances requires as much as 8 to 24 hours. A useful temperature range is from 125 to 225 C. The completion of the reaction of each addition of ethylene oxide in stepwise fashion ls usually indicated by the reduction or elimination of pressure. An amount conveniently used for each addition is generally equivalent to a mole or two moles of ethylene oxide per hydroxyl radical. When the amount of ethylene oxide added is equivalent to approximately 50% by weight of the original resin, 8. sample is tested for incipient hydrophile properties by simply shaking up in water as is, or after the elimination of the solvent if a solvent is present. The amount of ethylene oxide used to obtain a useful demulsifying agent as a rule varies from 70% by weight of the original resin to as much as five or six times the weight of the original resin. In the case of'a resin derived from para-tertiary butylphenol, as little as 50% by weight of ethylene oxide may give suitable solubility. With propylene oxide, even a greater 55 molecular proportion is required and sometimes when viewed in a comparatively thinlayer, for

a resultant of only limited hydrophile properties is obtainable. The same is true to even a greater extent with butylene oxide. The hydroxylated alkylene oxides are more eifective in solubiliz'ing properties than the comparable compounds in which no hydroxyl is present.

Attention is directed to the fact that in the subsequent examples reference is made to the stepwise addition of the alkylene oxide, such as ethylene oxide. It is understood, of course, there is no objection to the continuous addition of alkylene oxide until the desired stage of reaction is reached. In fact, there may be less of a hazard involved and it is often advantageous to add 70 to 1 ratio. Such moderate hydrophile character the fact that these remarkable oxyalkylated resins having surface activity show unusual properties as the hydrophile character varies from a minimum to an ultimate maximum. One should not underestimate the utility of any of these polyhydric alcohols in a surface-active or sub-surface-active range without examining them by reaction with a number of the typical acids herein described and subsequently examining the resultant for utility, either in demulsification or in some other art or industry as referred to elsewhere, or as a reactant for the manufacture of A few simple pare 0.5% and 5.0% solutions in distilled water,

as previously indicated. A mere examination of such series will generally reveal an approximate range of minimum hydrophile character, moderate hydrophile character, and maximum hydrophile character. If the 2 to 1 ratio does not show minimum hydrophile character by test of the solvent-free product, then one should test its capacity to form an emulsion when admixed with xylene or other insoluble solvent. If neither test shows the required minimum hydrophile property, repetition using 2 /2 to 4 moles per phenolic nucleus will serve. Moderate hydrophile character should be shown by either the 6 to 1 or 10 is indicated by the fact that the sol in distilled water within the previously mentioned concentration range is a permanent translucent sol instance the depth of a test tube. Ultimate hydrophile character is usually shown at the 15 to 1 ratio testin that adding a small amount of an insoluble solvent, for instance 5% of xylene, yields a'product which will give, at least temporarily, a, transparent or translucent sol of the kind just described. The formation of a permanent foam, when a 0.5% to 5.0% aqueous solution is shaken, is an excellent test for surface activity. Previous reference has been made to the fact that other oxyallwlating agents may require the use of increased amounts of alkylene oxide. However, if one does not even care to go to the trouble of calculating molecular weights, one can simply arbitrarily prepare compounds containing ethylene oxide equivalent to about 50% to by weight, for example 65% by weight, ofthe resin to be oxyethylated; a second ,It may be well to emphasize the fact that when 15 example using approximately 200% to 300% by Weight, and a third example using about 500% to 750% by weight, to explore the range of hydrophile-hydrophobe balance.

A practical examination of the factor of oxyalkylation level can be made by a very simple tee using a pilot plant autoclave having a capacity of about to gallons as hereinafter described. Such laboratory-prepared routine compounds can then be tested for :olubilit'y and, generally speaking, this is all that is required to give a suitable variety covering the lwdrophile-hydrophobe range. All these tests, as stated, are intended to be routine tests and nothing more. They are intended to teach a person, even though unskilled in oxyethylation or oxyaikylation, how to prepare in a perfectly arbitrary manner, a series of compounds illustrating the hydrophile-hydrophobe range.

If one purchases a thermoplastic or fusible resin on the open market selected from a suitable number which are available, one might have to make certain determinations in order to make the quickest approach to the appropriate oxyalkylation range. For instance, one should know (a) the molecular size, indicating the number of phenolic units; (b) the nature of the aidehydic residue, which =s usually CH1; and (c) the nature of the substituent, which is usually butyl, amyl, or phenyl. With such information one is in substantially the same position as if one had personally made the resin prior to oxyethylation.

For instance, the molecular weight of the internal structural units of the resin or the following over-simplified formula:

OH OH OH H H C C- H H R R B (11:1 to 13, or even more) is given approximately by the formula: (Moi. wt. of phenol -2) plus mol. wt. of methylene or substituted methylene radical. The molecular weight of the resin would be n times the value for the internal limit plus the values for the terminal The left-hand terminal wt of the above structural formula, it will be seen, is identical with the recurring internal unit except that it has one extra hydrogen. The right-hand terminal unit lacks the methylene bridge element. Using one internal unit of a resin as the basic element, a resin's molecular weight is given approximately by taking (11 plus 2) times the weight of the internal element. Where the resin molecule has only 3 phenolic nuclei as in the structure shown, this calculation will be in error by several per cent; but as it grows larger, to contain 6. 9, or 12 phenolic nuclei, the formula comes to be more than satisfactory. Using such an approximate weight, one need only introduce, for example, two molal weights of ethylene oxide or slightly more, per phenolic nucleus, to produce a product of minimal hydrophile character- Further oxyalkylation gives enhanced hydrophile character. Although we have prepared and tested a large number of oxyethylated products oi the type described herein, we have found no instance where the use of less than 2 moles of ethylene oxide per phenolic nucleus gave desirable products.

Examples it through 18b, and the tables which appear in columns 51 through 56 of our said Patent 2,499,370 illustrate oxyalkylation products from resins which are useful as intermediates for producing the esterified products used in accordance with the present application, such examples giving exact and complete details for carrying out the oxyalkylation procedure.

The resins, prior to oxyalkylation, vary from tacky, viscous liquids to hard, high-melting solids. Their color varies from a light yellow through amber, to a deep red or even almost black. In the manufacture of resins, particularly hard resins, as the reaction progresses the reaction mass frequently goes through a liquid state to a sub-resinous or semi-resinous state, often characterized by being tacky or sticky, to a final complete resin. As the resin is subjected to oxyalkylation these same physical changes tend to take place in reverse. If one starts with a solid resin, oxyalkylation tends to make it tacky or semi-resinous and further oxyalkylation makes the tackiness disappear and changes the product to a liquid. Thus, as the resin is oxyalkylated it decreases in viscosity, that is, becomes more liquid or changes from a. solid to a liquid, particularly when it is converted to the water-dispersible or water-soluble stage. The color of the oxyalkylated derivative is usually considerably lighter than the original product from which it is made, varying from a pale straw color to an amber or reddish amber. The viscosity usually varies from that of an oil, like castor oil, to that of a thick viscous sirup. Some products are waxy. The presence of a solvent, such as 15% xylene or the like, thins the viscosity considerably and also reduces the color in dilution. No undue significance need be attached to the color for the reason that if the same compound is prepared in glass and in iron, the latter usually has somewhat darker color. If the resins are prepared as customarily employed in varnish resin manufacture, i. e., a procedure that excludes the presence of oxygen during the resinification and subsequent cooling of the resin, then of course the initial resin is much lighter in color. We have employed some resins which initially are almost water-white and also yield a lighter colored final product.

Actually, in considering the ratio of alkylene oxide to add, and we have previously pointed out that this can be pre-determined using laboratory tests, it is our actual preference from a practical standpoint to make tests on a small pilot plant scale. Our reason for so doing is that we make one run, and only one, and that we have a complete series which shows the progressive eiTect of introducing the oxyalkyiating agent, for instance, the ethyleneoxy radicals. Our preferred pro cedure is as follows: We prepare a suitable resin, or for that matter, purchase it in the open market. We employ 8 pounds of resin and 4 pounds of xylene and place the resin and xylene in a suitable autoclave with an open reflux condenser. We prefer to heat and stir until the solution is complete. We have pointed out that soft resins which are fluid or semi-fluid can be readily prepared in various ways, such as the use of orthotertiary amylphenol, ortho-hydroxydiphenyl, ortho-decylphenol or by the use of higher molecular weight aldehydes than formaldehyde. If such resins are used, a solvent need not be added but may be added as a matter of convenience or for comparison, if desired. We then add a catalyst, for instance, 2% of a to 30% solution, and remove the water of solution or formation. We then shut oil? the reflux condenser and use the equipment as an autoclave only, and oxyethylate until a total of 60 pounds of ethylene oxide have been added, equivalent to 150% of the original resin. We prefer a 'temperatureof about 150 C. to 175 C. We also take samples at intermediate point as indicated, in the following table:

. assesses? present and the series with xylene removed.

Mere visual examination of any samples in solution maybe sufficient to indicate hydrophile of caustic soda, in the form tion of 2 or 3 moles of the oxyalkylating agent per phenolic nucleus, particularly ethylene oxide, gives a surface-active reactant which is perfectly satisfactory, while more extensive oxyethylation yields an insoluble rubber, that is, an unsuitable reactant. It is obvious thatthis present proce dure of evaluating trifunctional phenol tolerance is more suitable than the previous procedure.

-It may be well to call attention to one result which may be noted in a long drawn-out oxyalkylation, particularly oxyetbylation, which would not appear-in a normally conducted reaction. Reference has been'made to cross-linking and its eifect on solubility and also the fact that, if carried far enough, it causes incipient stringiness, men pronounced stringiness, usually followed by a semi-rubbery or rubbery stage. Incipient stringiness, or even pronounced stringiness,'or even the tendency toward a rubbery stage, is not objectionable so long as the final product is still hydrophile and at least sub-surface-active. Such material frequently is best mixed with a polar solvent, such as alcohol or the like, and

character or surface activity, i..e., the product is soluble, forming a colloidal $01, or the aqueous so- I lution foams or showsemulsifying property.- All, these properties are related through adsorption.

at the interface; for example, a gas-liquid interface or a liquid-liquid interface. It desired,-surface activity can be measured in any one of the I usual ways using'a DuNouy tensiometer or dropping pipette, or any other procedure for measura ing interfacial tension. Such tests are conventional and require'no further description. Any

compound having sub-surface-activity, and all I derived from the same resin and oxyalkylated to a greater extent, i. e., those having a greater proportion of alkylene oxide, are useful as polyhydric reactants for the practice of this invention.

Another reason why we prefe to use a pilot plant test of the kind above described is that-we "can use the same procedure to evaluate tolerance towards a trifunctional phenol such as hydroxybenzene or metacresol satisfactorily. Previous reference has been made to the fact that one can conduct a laboratory scale test which will indicate whether or not a resin, although soluble in solvent, will yield an insoluble rubbery product, 'i. e., a product which is neither hydrophile nor surface-active, upon oxyethylation, particularly extensive oxyethylation. It is also obvious that one may have a solvent soluble resin derived .from a mixture of phenols having present 1% or 2% of a trifunctional phenol which will result in aninsoluble rubber at the ultimate stages of oxy etbylation but not in. the earlier stages. In other .-w ords, with resins from some such phenols; addi,

, alkylation as rapidly as possible and then propreferably an alcoholic solution is used. The point which we want to make here, however, is this: stringiness or rubberization at this stage may possibly be the result of etherification. Obviously if a difunctional phenol and an aidehyde produce a non-cross-linked resin molecule and if such molecule is oxyalkylated so as to introduce ,a plurality of hydroxyl groups in each molecule, then and in that event if subsequent .etherification takes place, one is going to obtain cross-linking in the same general way that one .would obtain cross-linking in other resinification reactions. Ordinarily there is little or no tendency toward etherification during the oxyalkylation step. If it does take place at all, it is only to an insignificant and undetectable degree. However, suppose that a certain weight of resin is treated with an equal weight of, or twice its weight of, ethylene oxide. This may be done in a comparatively short time, for instance, at or C. in 4 to 8 hours, or even less. On the other hand, if in an exploratory reaction, such as the kind previously described, the ethylene oxide were added extremely slowly in order to take stepwise samples, so that the reaction required 4 or 5 times as long to introduce an equal amount of ethylene oxide employing the same temperature, then 'etheriiication might cause stringiness or a su gestion of rubberiness. For this reason if in an exploratory experiment of the kind previously described there app ars to be any stringiness or rubberiness, it may be well to repeat the experiment and reach the intermediate stage of oxyceed slowly beyond this intermediate stage. The entire purpose of this modified procedure is to cut down the time of reaction so as to avoid etheriflcation if it be caused by the extended time period.

It may be well to note one peculiar reaction sometimes noted in the course of oxyalkylation, particularly oxyethylation, of the thermoplastic resins herein described. This eflect is noted in a case where a thermoplastic resin has been oxyalkylated, for instance, oxyethylated, until it gives a perfectly clear solution, even in the presence of some accompanying water-insoluble solvent such as, 10% to 15% of xylene. Further oxyalkylation, particularly oxyethylation, may

.then yield a. product which, instead of giving a clearsolution as previously, gives a very milky solution suggesting that some marked change has taken place. One explanation of the above change is that the structural unit indicated in the following way where 8n is a fairly large number, for instance, 10 to 20, decomposes and an oxyalkylated resin representing a lower degree of oxyethylation and a less soluble one, is generated and a cyclic polymer of ethylene oxide is produced, indicated thus:

I I O H J MEM owmslal This fact, of course, presents no difilculty for the reason that oxyalkylation can be conducted in each instance stepwise, or at a gradual rate, and samples taken at short intervals so as to arrive at a point where optimum surface activity or hydrophile characted is obtained if desired; for products for use as polyhydric reactants in the practice of this invention, this is not necessary and, in fact, may be undesirable, i. e., reduce the efficiency of the product.

We do not know to what extent oxyalkylation produces uniform distribution in regard to phenolic hydroxyls present in the resin molecule. In some instances, of course, such distribution can not be uniform for the reason that we have not specified that the molecules of ethylene oxide, for example, be added in multi les of the units present in the resin molecule. This may be illustrated in the following manner:

Suppose the re in happens to have five phenolic nuclei. If a minimum of two moles of ethylene oxide per phenolic nucleus are added. this would mean an addition of 10 moles of ethylene oxide, but suppose that one added 11 mo es of ethylene oxide, or 12, or 13, or '14 moles: obviously, even assuming the most uniform distribution possible, some of the polyethyleneoxy radicals would con tain 3 ethyleneoxy units and some would contain 2. Therefore, it is im ossible to specify uniform distribution in regard to the entrance of the ethylene oxide or other oxyalkylating agent. For that matter, if one were to introduce moles of ethylene oxide there is no way to be certain that all chains of ethyleneoxy units would have 5 units: there might be some having, for example, 4 and 6 units, or for that matter 3 or '7 units. Nor is there any basis for assuming that the number of molecules of the oxyalkylating agent added to each of the molecules of the resin is the same, or different. Thus, where formulae are given to illustrate or depict the oxyalkylated products, distributions of radicals indicated are to be statistically taken. We have, however, included specific directions and specifications in regard to the total amount of ethylene oxide, or total amount of any other oxyalkylating agent, to add.

In regard to solubilit of the resins and the oxyalkylated compounds. and for that matter derivatives of the latter, the following should be noted. In oxyalkylation, any solvent employed should be non-reactive to the alkylene oxide employed. This limitation does not apply to solvents used in cryoscopic determinations for obvious reasons. Attention is directed to the fact that various organic solvents may be employed to 28 verify that the resin is organic solvent-soluble. Such solubility test merely characterizes the resin. The particular solvent used in such test may not be suitable for a molecular weight determination and, likewise, the solvent used in determining molecular weight may not be suitable as a solvent during oxyalkylation. For solution of the oxyalkylated compounds, or their derivative a great variety of solvents may be employed, such as alcohols, ether alcohols. cresols, phenols, ketones, es ters, etc., alone or with the addition of water. Some of these are mentioned hereafter. We prefer the use of benzene or diphenylamine as a solvent in making cryoscopic measurements. The most satisfactory resins are those which are soluble in xylene or the like, rather than those which are soluble only in some other solvent containing elements other than carbon and hydrogen. for instance, oxygen or chlorine. Such solvents are usually polar, semi-polar. or slightly polar in nature compared with xylene, cymene. etc.

Reference to cryoscopic measurement is concerned with the use of benzene or other suitablecompound as a solvent. Such method will show that conventional resins obtained, for example. from para-tertiaryamylphenol and formaldehyde in presence of an acid catalyst, will have a molecular weight indicating 3, 4. 5 or somewhat greater number of structural units per molecule. If more drastic conditions of resinification are employed or if such low-stage resin is subjected to a vacuum distillation treatment as previously described, one obtains a resin of a distinctly higher molecular weight. Any molecular wei ht determination used, whether cryoscopic measurement or otherwise, other than the conventional cryoscopic one employing benzene, should be checked so as to insure that it gives consistent values on such conventional resins as a control. Frequently all that is necessary to make an approximation of the molecular weight range is to make a comparison with the dimer obtained by chemical combination of two moles of the same phenoL-and one mole of the same aldehyde under conditions to insure dimerization. As to the preparation of such dimers from substituted phenols, see Cars well, Phenoplasts, page 31. The increased viscosity, resinous character, and decreased solubility, etc., of the higher polymers in comparison with the dimer, frequently are all that is required to establish that the resin contains 3 or more structural units per molecule.

Ordinarily, the oxyalkylation is carried out in autoclaves provided with agitators or stirringdevices. We have found that the speed of the agitation markedl influences the reaction time. In some cases, the change from slow speed agitation, for example, in a laboratory autoclave agitation with a stirrer operating at a speed of to 200 R. P. M., to high speed agitation, with the stirrer operating at 250 to 350 R. P. M., reduces the time required for oxyaikylation by about one-half to 76 two-thirds. Frequently xylene-soluble products which give insoluble products by procedures employing comparatively slow speed agitation, give suitable hydrophile products when produced by similar procedure but with high speed agitation, as a result, we believe, of the reduction in the time required with consequent elimination or curtailment ofopportunity for curing or etherization. Even if the formation of an insoluble prodnet is not involved, it is frequently advantageous to speed up the reaction, thereby reducing production time, by increasing agitating speed. In large scale operations, we have demonstrated that quired to dissipate heat of reaction; thus, if there is a temperature drop without the use of cooling economical manufacturing results from continuous oxyalkylation, that is, an operation in which the alkylene oxide is continuously fed to the reaction vessel. with high speed agitation, i. e., an agitator operating at 250 to 350 R. P. M; Continuous oxyalkylation, other conditions being the water or equivalent, .or if there is no rise in temperature without using cooling water control, careful investigation should be made.

In the tables immediately'following, we are showing .the 'maximum temperature which is the .operating temperature. In other words, by experience we have found that if the initial reactants are raised to the indicated temperature and then if ethylene oxide is added slow- 1 ly, this temperature is maintained by cooling same. is more rapid than batch oxyalkylation,

but the latter is ordinarily more convenient for laboratory operation.

Previous reference has been made to the fact that in preparing esters or compounds of the kind herein described, particularly adapted for demulsiiication of water-in-oil emulsions, and for that matter for other purposes, one should make a complete exploration of the wide variation in hydrophobe-hydrophile balance aspreviously referred to. It has been stated, furthermore, that this hydrophobe-hydrophile balance of the oxyalkylated resins is imparted, as far as the range of variation goes, to a greater or lesser extent to the herein described derivatives. This means that one employing the present invention should take the choice of the most suitable derivative selected from a number of representative comequipment, for instance, an autoclave having a.

capacity of approximately three to five gallons.

' We have made a single run byappropriate selections in which the molal ratio of resin equivalent to ethylene oxide is one to one, 1 to 5, 1 to 10, l to 15, and 1 to 20. Furthermore, in making these particular runs we have used continuous" addition of ethylene oxide. In the continuous addition of ethylene oxide we have employed either a cylinder of ethylene oxide without added nitrogen, provided that the pressure of the ethylene oxide was sufliciently, great to pass into the autoclave, or else we have used an arrangement which, in essence, was the equivalent of an ethylene oxide cylinder with a means for injectwater until' the 'oxyethylation' iscomplete. We have also indicated the maximum pressure that we obtained or the pressure range. Likewise, we have indicated the time required to inject the ethylene oxide as well as a brief note as to the solubility of the product at the end of the oxyethylation period. As one period ends it will be noted we have removed part of the oxyethylated mass to give us derivatives, as therein described; the rest has beensubjected to further treatment. All this is apparent by examining. the columns headed Starting mix," Mix at end of reaction, Mix whichis removed for sample, and Mix which remains as next starter."

The resins employed are prepared in the manner described in Examples 1a through 103a of our said Patent 2,499,370, except that instead of being prepared on a laboratory scale they were prepared I in 10 to 15-gallon electro-vapor heated synthetic change is one operation. The solvent used in. each instance was xylene.

resin pilot plant reactors, asmanufactured by the Blaw-Knox Company, Pittsburgh, Pennsylvania, and completely described in their bulletin No. 2087 issued in 1947, with specific reference to specification No. 71-3965.

For convenience, the following tables give the numbers of the" examples of our said Patent 2,4.99370 in which the preparation of identical resins on laboratory scale are described. It is understood that in the following examples, the

This solvent is particularly satisfactory for the reason-that it can be removed readily by'distillation or vacuum distillation. In these continuous ing nitrogen so as to force out the ethylene oxide in the manner of an ordinary seltzer bottle, combined with themeans for either weighing the cylinder or measuring the ethylene oxide used volumetrically. Such procedur and arrangement for injecting liquids is, of course, conventional. The following data sheets exemplify such operations, i. e., the combination of both continuous agitation and taking samples so as to give five different variants in oxyethylation. In adding ethylene oxide continuously, there is one precaution which must be taken at all times. The addition of ethylene oxide must stop immediately if there is any indication that reaction is stopped or, obviously, if reaction is not started at the beginning of the reaction period. Since experiments the speed of the stirrer in the autoclave was 250 R. P. M.

In examining the subsequent tables it will be noted that if a comparatively small sample is taken at each stage, for instance, to one gallon, one can proceed through the entire molal stage of 1 to l, to 1 to 20, withoutremaking at any intermediate stage. This is illustrated by Example 10%. In other examples we found it desirable to take a larger sample, for instance, a 3-gallon sample, at an intermediate stage. As a result it was necessary in such instances to start with a new resin sample in order to prepare sufshows that the starting mix was not removed from a previous sample.

with'respect to the size of the Phenol for resin: Para-tertiary amylphenol Aldehyde for resin: Formaldehyde Date, June 22, 1948 [Resin made in pilot plant size batch, approximately-25 pounds, corresponding to 3a of Patent 2,499,370 but this batch designated 1040.]

Mix which is Mix Which Re- Starting Mix g figg or Removed for mains as Next Sample Starter Max. Max. Time Pressure Tempgra- Solubility Ibs. Lbs. Lbs l b s. abs. Lbs girls. I gs. Lbs 18.1519. abs. Lbs

o- Resesos- 0- esvent in Eto vent in Eto vent in Eto vent in Eto First Stage Resin to EtO-... Molal Ratio 1:1-- }14 15.75 0 14.25 15.75 4.0 3.35 3.65 1.0 10.9 12.1 3.0 80 150 M I Ex. No. 1040.--"

Second Slope Resin to EtO.... Molai Ratio 1 10 9 12.1 3.0 10.9 12.1 15.25 3.77 4.17 5. 31 7.13 7.93 9.94 158 36 81. Ex. No. 1055---" Thrrd Stage Resin to EtO Moiai Ratio 1:10- 7 13 7.93 9.94 7.13 7.93 19.09 3.29 3.68 9.04 3.84 4.25 10.65 60 173 )6 F8 Ex. No. 10Gb"--- Fourlh Stage Resin to EtO- Molai Ratio 1 5- 3 84 4.25 10.65 3.84 4.25 16.15 2.04 2.21 8.55 1.80 2.04 7.00 220 160 16 R8 EX.N0.1070--..

Fifth Stage Resin to EtO- M0181 Ratio 1:20. 1 2.04 7.60 1.80 2.04 10.2 )6 QB EX. N0. l08b- I=Inso1uble. ST=Siight tendency toward becoming soluble. FS=Falrly soluble. RS=Readily soluble. QS=Quite soluble.

' Phenol for resin: Nonylphenol Aldehyde for resin: Formaldehyde Date, June 18, 1948 [Resin made in pilot plant size batch, approximately 25 pounds, corresponding to 70a of Patent 2,499,370 but this batch designated 10911.]

M1! which 18 MIX which R0- Starting Mix Mk g ggg or Removed tor mains as Next Sample Starter Mm Mam Pressure Tempsra- 3:? Solubility lbls. libs. Lbs Ibia. abs. Lbs Ibia. kbs. Lbs 1 .11 5. abs. Lbs

0- es- 0- es 0- es- 0- esvent in vent in Eto vent in Eto vent in Eto First Stage Resin to Et0 Molal Ratio 1:1 15 0 Ex. No. 1095".--

Second Stage Resin to 120.... Molal Ratio 1:5 10 EX. N0. 1100----- Third Stage Resin to EtO Molal Ratio 1:10. 7 27 Ex. No. 1115.....

Fourth Stage Resin to Et0 Molnl Ratio 1:15. Ex. No. 1125"--- Fifth Stage Resin to EtO.-.. M0181 Ratio 1:20- 2.10l 2.10 0.00 2.10 2.10 8.00 220 183 36 V8 Ex. No. 1130-- S=Soluble. ST=S1ight tendency toward solubility. DT=Deflnite tendency toward solubility. VS=Very soluble.

Phenol for resin: Pam-odylphenol Aldehyde for resin: Formaldehyde Date,Iuno23.24,19l8 i V v [Resin made In pilot plant size batch, approximately 25110111165, corresponding t 8:: of Patent 2,499,370 but this batch' designated 11411.]

- r 1 Y 'MkWhleh 13-, Mlx which Ro- Starting Ml: Y gg ggg Re'movad [or mains as Next I V Sample Starter Mu Time.

Pm Tampsmmm Solubility Lbs. L1 1. Lbs Lbs. Lbs. Lb Lbs. Lbs. Lb Lbs. Lbs. y 801- m s01- 11.1.0- a- Resa- Sol- Rea- E vent in vent in V vent ln vent in t l 115tstaae' RasintoEt0---- Molal Ratio 1-1 14.2 15.8 o 14.2 158 5.25 0.1 3.4 0.15 11.1 124 25 50 150 144, N Ex. No.1l4b v Second Stage 12430101111 f M0181 R0010 1 =5-- 11.1 12.4 2.5 11.1 12.4 125 1.0 7.82 1.08 4.1 4.55 4021 1001 V 111 44 58 Ex. No. 1l6b- V fllrd Stag:

l1 4l a l i5 }&6l 1 0 004 130 150 1 o 1m 1 B 111.110.1100-- I m Fourth Stage I 'ReslntoEtQ.-- I

100111 Ratio-1:15- 440 4.0 o 4.4 40 '14s 4m 1 14 vs Ex. No.117b- F1115 sa ReslntoEt0---- Molal Banal-- 4.1 4.50 4.02-4.1- 4.55 18.62 250 1 44 vs Ex. No.118b V j I I B-Solublo. NB-Not 1010015. SB-Somewhat soluble. vs-v 1010011.

7 Phenol for "5 in: Menthylphenol Aldehudg for rain: Formaldehyde 1304 111191143.1045 v I 110 111 1 1100 in 0105 11m approximately pounds, cop-expanding to 00 of Patmt 2,400,310 but an; batch designated 1105.1

I r Mlxwhichls ,Mix wmchke- StartingMix mg: of Removed for mainsasNext i r I .Bample Starter Ma I Pressure Tempgra- :2? Solubility 1 2 Lbs. 1 2 21. Lbs 181215. 11525. Lbs 1 .11 1. Ifibs. Lbs

n s w vent in Eto vent vent in E) vent in Eto ResintoEt0--- I Molal Ratlol:l-- 11.05l1035 0 13.05 1035 '00 0.55 11.45 21 4.1 4.0 0.0 00 150 114 NS Ex. No. 1190.-.-- v

Second-91002 V V ResintoEtO---. V Mala] R8$101:5-- 10 12 0 1o 12 10.15 402 542 4.81 548 058 5.04 1401 154, s Ex. 010.1205"--- 11:14am;

I 1a0 111 194, vs

. 115411100210 5 Molal Batlol- 210 3.12 am 3.10 0.12 12m am 34 vs Ex; 80.1240- I I v 3 mm p g-K 00 1 1 VS-Vkynolable.

Phenol for resin: Para-secondary butylphenol Date. July 14 15. 1948 [Resin made in pilot plant size batch. approximately 25 pounds, corresponding to 2 a! Patent m but this batch dnsignatad 1244.]

Aldehyde for rain: Formaldehyde Mix Whichis MixWhichBp- Starting Mix mg: Removed for mains m Next Sample amm- Ma Ma Time, Prasun Temp srahm Solubility w a m is: a m .2: .2; w

esa vent in Em vent in Em vent in vent in Etc First Stage Resin to Et0.... Moiai Rati01:1-- 14.45 15.55 0 14.45 15.55 4.5 5.97 6.38 1.75 8.48 117i 231! ml 150 5i: NB Ex.No.124b

Second Slag: Rain :0 mo..- I MolalRaflo l:5 8.48 9.17 2.50 8.48 0.17 10.0 5.83 0.32! 11.05i 265i 285! 4.05l 05 188 M 88 Ex. No. 1250-..-

Third Stage Resin to no... Molai Ratio 1:10. 4.82 5.18 0 4.82 5.18 14.25 mm 183 )6 8 Ex.No.126b

Fourth Stage Resin to Et0 Moial Ratio 1:15- 3.85 4.15 0 3.85 4.15 17.0 mi 18) 34 VS Ex. No. 1270...... I I

Fifth Stage Resin to Et0. i Molai Bati01z20. 2.65 285 4.95 2.65 2.85 15.45 N 170 Ml VB Ex.No.128b. I I I I B soluble. NS -Not soluble. S8=Somewbat soluble. VB-Very aaluhia.

P henol for resin: M enthyi -Aldehydc for resin: Propionaldehyde Date, August 12-13, 1848 [Resin made on pilot plant size batch, approximately pounds, em-mponding to 81a of Patent 2,499,310 but this batch dedgnated 1291.]

Mix Whichis MlxWhichBe- Starting Mix mg: of Removed for mainsaNm Sample Starter m M Pmsum Tempem- Solubility lhs.sq in. me, C Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Soi- Res- Egg Bol- Res- Egg 801- ms- 801- m 23- vent in vent in vent in vent in Firat Stage Resin to Et0..... Molai Ratio 1:1-- 128 17.2.. 12.8 17.2 2715 4.25 5.7 0.95l 8.55 11.51 LN 11!]! 150 Ml Not soiubia. Ex. No. 1290 Second Stage Resin to EtO.. I Mala! Ratio 8.55 11.50 1.80 8.55 11.50 9.3 4.78l 6. 5.2 3.7!! 508i um ml 170 )6! Somewhat Ex. No. 130b soluble.

Third Stage Resin to Et0 Moiai Ratio 1:10- 3.77 5.08 4.10 3.77 5.08 13.1 lml 182i M: Solublo. Ex. No. 131b Fourth Stage ResintoEt0... Molai Ratio 1:15- 6.2 7.0 5.2 7.0 17.0 3.10I 4.17 10.13l 2.10 2.83 6.87 m 182 M 701750101116. Ex. No. 132b I Fifth Stage ia l fi t qfiI no 2831185210 283 9.12 5011:

o a 10 EX.N0.133b I I r 1 I I I I I M Phenol for rein'n: Para-tertiary amylphenol Aldehyde for resin: Furfuml Date, August 27-31, 1948 v I [Resin made on pilot plant size batehQappioximateIyPfi pounds, corresponding to 424: of Patent 2,499.370 but this batch designated as 13441.]

Mk at End Mix which is M1: Which Re- Btartin Mix Removed for mains as Next 8 negation Sample Starter M I ax. Max. Tun Pressure Tempgrahm Solubility l b s. 115. Lbs gbls. libs. Lbs Ibls. gm. Lbs gb abs. Lbs -fi Q 0 eso eso eso esvent in Eto vent in Em vent in Em vent in Eto First Stage }11.2 18.0 11.2 18.0 3.5 2.75 4.4 0.85 8.45 13.6 2.65 v I '120 135 56 Not soluble.

Second Stage Resin to 1 Molai Ratiol:5- 8.45 13.6 2.65 8.45 13.6 1265 -5.03 8.12 7.55 3.42 5.48 5.10 150 )4 Somewhat Ex. N 0. b v j soluble.

Third Stage Resin to Et0 1 v f I 1 Molal Ratio 1:10 4 5 8.0 4.5 8. 0 14.5. 2.45 4.35 7.09 2.05 3.65 6.60 180 163 $4 .Soluble. Ex. No. 136b. v v l Fourth Stage Resin to EtO V I V V Molal Ratio1:15 3. 42 5.48 5.10 3.42 5.48 15.10 V I 180 188 $6 verysoluble. Ex. N0. 1370 I I Fifth Stage Resin to EtO..-.. I v V I I I Molal Ratio 1:20.- 2. 05 3.65 6.60 2.05 3.65 13. 35 I v 12) 125 M verysoluble. Ex. No. l38b I I I w I v 1 P7191101 f il .Menthyl Aldehyde for resin: Fw fural V Date, Sept. 23-24,194s v V [Resin made on pilot size b etch approxinnete lv 25 ponnds, correponding to 89a of P atent 2,499,370 but this bafch designated as 13911.]

' 1 Mix whichis- MixWhichRe- Sta'rting Mix v I ggf fi g Removed r01- mains as Next v Sample .Starter I I I v 1 Max. Max. Tim v V I o I-"ressurev Tempgm- Solubility 1 .11 5. Lbs. Lbs gbls. m. I b s. abs. Lbs I 1 .2 5. abs. Lbs n I 0 Res-' v o es- 0 es es- I vent in Em vent in vent in mo 'vent in J V r i I First Stage Resin to Et0 I v v I I I Mole] Ratioi 1 }10.25 17.75 10.25 17.75 2.5 2.65 4.60 0.65 7.6 13.15 1.85 90 150 361 Not soluble. Ex. No. 139b V I Second Stan:

Resin to Et0 I V v M0181 Ratio 1:5 76 13.15 1.85 7.6 13.15 9.35 5.2 9.00 6.40 2.4 4.15 2.95 80 177 V I Somewhat Ex. N 0. b I I 801ub 1e.

Third Slaqe Resin1oEtO. g V II V o I Y- M0181 Ratio 1210"} 4 22 6.98 4.22 6.98 10.0 00 I 165 M Soluble. Ex. No. 14111-"-.- I v i r I I Fourth Stage I v Resin m Eton--- Q i v I I I V I Moial Ratio 1:15 3. 76 6. 94 3. 76 6. 24 13.25 v 100 171 'Ml Verysolubie. Ex. No. 1425------ V V II I V 7 Fifth Stage I Resin to EtO. l I 1 0 I v Molal Rmiol: 2 4 4.15 I 2.95 2.4 I 4.15 11.70 I V 90 $6 Verysoluble- Ex.i\'0.'143h w v V Date. October 7-8. 1048 Phenol for resin: Para-octyl R sin ads on ilot lant size batch, approximately 25 pounds, oorrespondlng to 4241 at Patent 2,499,370 with 200 parts by weight oi commercial I e m garactylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 144a.1

Mix which is Mix Which Re- Starting Mix fig ggg Removed for mains as Next Sample Starter Max. Max. me Pressure 'lemp erahm Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs.

vent in vent in vent in vent in First Stage Resin to Et0--- Molal Ratio 1:1 12.1 18.6 121 18.6 3.0 5.38 8.28 1.34 6.72 10.32 1.66 80 150 Ma Insoluble. Ex. No. 1445---" Second Stage Slight tend- ResintoEtO. one to- Molal Ratio 1:5" 9.25 14.25 9.25 14.25 11.0 3.73 5.73 4.44 5.52 8.52 6.56 100 177 i: war Ex. No. 1455.--" coming solublo. Third Stage Resin to EtO- Moial Ratio 1- 6.72 10.32 1.66 6.72 10.32 14.91 4.97 7.62 11.01 1.75 2.70 3.90 85 182 M Fairly solu- Ex. No. 1465 ble.

Fourth Stage Resin to EtO-- Molal Ratio 1:15. 5.52 8.52 6.56 5.52 8.52 19.81 100 176 v )4 Readily col- Ex. No. 1475..... able.-

Fifth Stage Resin to Et0 Moial Ratio 1:20- 1.75 2.70 3.90 1.75 2.70 8.4 80 160 M Quite solu- Ex. No. 1485..... bio.

Date, October 11-13, 1948 Phenol for resin: Para-phenyl Aldehyde for resin: Furfural [Resin made on pilot lant size batch, approximately 25 pounds, corresponding to 42a of Patent 2.490.370 with 170 parts by weight of commercial parap enylphenol replacing 164 parts by weight of para-tertiary amylphenol but this batch designated as 1490.]

1 Mix Which is Mix Which Re- Starting Mix g fgg or Removed for mains as Next Sample Starter Max. Max. Time Pressure 'Iemp rahm Solubility Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. Lbs. S01- Res- 25- 801- Resg g? Res- 801- Resg vent in vent in vent in vent in First Stage Resin tn EtO- Molal Ratio 1- 13.9 16.7 13.9 16.7 3.0 3. 50 4. 0.80 10.35 12. 2.20 K Insoluble. Ex. No. 1496 Second Stage Resin w 120-.-. tend Molal Ratio 1:15-- }1o.35 1245 220 10.35 1245 12.20 5.15 6.19 6.06 5.20 0.20 0.14 so 183 34 f EX. No.150b.----

bility. Third Stage Resin to EtO-.- Molal Ratio 1:10- 8.90 10. 7 690 10.70 19.0 5.30 6.38 11.32 3.60 4. 32 7.68 90 193 M: Fairly solu- Ex. No. 151b-..-- bio.

Fourth Stage Resin to EtO.-.. Moial Ratio 1:15. 5. 20 6.26 6.14 5.21 6.26 16. 100 171 )6 Readily sol- Ex. No. 152b--.- uble.

Fifth Stage Resin to EtO- Molai Ratio 1: 3.60 4.32 7.68 3.60 4.32 15.68 Sample somewhat rubbery and gelat- 210 2 Ex. No. 1535-. l inous but fairly soluble l I 

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE CHARACTERIZED BU SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFIER INCLUDING A HYDROPHILE ESTER IN WHICH THE ACYL RADICAL IS THAT OF THE FATTY ACID OF DRASTICALLYOXIDIZED DEHYDRATED CASTOR OIL, AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILE POLYHYDRIC SYNTHETIC PRODUCTS; SAID HYDROPHILE POLYHYDRIC PRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE AND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANIC SOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN, SAID RESIN BEING DERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVE TOWARD SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIAL ABSENCE OF TRIFUNCTIONAL PHENOLS; SAID PHENOL BEING OF THE FORMULA 